US20090149684A1 - Oligomerization of hydrocarbons - Google Patents
Oligomerization of hydrocarbons Download PDFInfo
- Publication number
- US20090149684A1 US20090149684A1 US11/951,863 US95186307A US2009149684A1 US 20090149684 A1 US20090149684 A1 US 20090149684A1 US 95186307 A US95186307 A US 95186307A US 2009149684 A1 US2009149684 A1 US 2009149684A1
- Authority
- US
- United States
- Prior art keywords
- accordance
- oligomerization
- range
- zeolite
- olefins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 116
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 108
- 150000001336 alkenes Chemical class 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 230000003606 oligomerizing effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 44
- 239000010457 zeolite Substances 0.000 claims description 37
- 229910021536 Zeolite Inorganic materials 0.000 claims description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 230000008929 regeneration Effects 0.000 claims description 31
- 238000011069 regeneration method Methods 0.000 claims description 31
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052680 mordenite Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 15
- 239000003502 gasoline Substances 0.000 claims description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 11
- 239000004711 α-olefin Substances 0.000 claims description 11
- 238000006317 isomerization reaction Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 7
- 239000001282 iso-butane Substances 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 10
- 239000012530 fluid Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 5
- 235000013847 iso-butane Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GPDWNEFHGANACG-UHFFFAOYSA-L [dibutyl(2-ethylhexanoyloxy)stannyl] 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)O[Sn](CCCC)(CCCC)OC(=O)C(CC)CCCC GPDWNEFHGANACG-UHFFFAOYSA-L 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- -1 metal chlorides Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- YUHZIUAREWNXJT-UHFFFAOYSA-N (2-fluoropyridin-3-yl)boronic acid Chemical class OB(O)C1=CC=CN=C1F YUHZIUAREWNXJT-UHFFFAOYSA-N 0.000 description 1
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical class CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical class CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/185—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- C07C2529/22—Noble metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
- C10G2300/1092—C2-C4 olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/22—Higher olefins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates generally to processing hydrocarbon-containing streams.
- the invention concerns processes for the oligomerization of hydrocarbon-containing streams.
- RVP Reid Vapor Pressure
- the Reid Vapor Pressure is a measure of the vapor pressure of gasoline, volatile crude oils, and other volatile petroleum products determined at approximately 38° C.
- EPA Environmental Protection Agency
- VOCs Volatile organic compounds
- Another embodiment of the invention is a process which comprises, consists of, or consists essentially of:
- Still another embodiment of the invention is a process which comprises, consists of, or consists essentially of:
- FIG. 1 depicts an oligomerization process system.
- FIG. 2 depicts a hydrocarbon processing and separation system.
- FIG. 3 is a graph plotting the weight percent of olefin conversion vs. time on-stream.
- One embodiment of the present invention is a process comprising, consisting of, or consisting essentially of:
- any zeolite-containing catalyst which is effective for the oligomerization of hydrocarbons can be used.
- the molar ratio of SiO 2 to Al 2 O 3 in the crystalline framework of the zeolite is in the range of from about 10:1 to about 150:1.
- the molar ratio of SiO 2 to Al 2 O 3 in the zeolite framework can also be in the range of from about 30:1 to about 100:1.
- Examples of zeolites that can be used include, but are not limited to mordenites.
- mordenites that can be used include but are not limited to Mordenite 40, Mordenite 90 and their hydrogen-promoted counterparts.
- any olefin can be oligomerized by the process of the present invention.
- the olefins have in the range of from 2 to 20 carbon atoms per molecule.
- the olefins can also have in the range of from 3 to 6 carbon atoms per molecule, and, additionally, the olefins can have 4 to 5 carbon atoms per molecule.
- the oligomerization reaction conditions in the oligomerization reaction zone include a temperature in the range of from about 35° C. to about 260° C.
- the temperature can also be in the range of from about 65° C. to about 150° C., and, additionally, the temperature can be in the range of from 90° C. to 130° C.
- the oligomerization reaction conditions also include a pressure in the range of from about 100 psi to about 800 psi.
- the pressure can also be in the range of from about 300 psi to about 500 psi, and, additionally, the pressure can range from 200 psi to 600 psi.
- the desired pressure maintains the process stream in the liquid form.
- the zeolite Before contacting the zeolite catalyst with olefins in an oligomerization zone, the zeolite can optionally be treated with one or more metal compounds in order to increase the acidity of the zeolite.
- the zeolite can be treated with compounds containing metals selected from the group consisting of zinc, cadmium, copper, silver, gold, gallium, indium, silicon, germanium, and tin. Generally, the compound contains zinc or tin.
- the metal compound can be incorporated into or onto the zeolite.
- One method of incorporating is to impregnate using any standard incipient wetness impregnation technique (i.e.
- Metal containing compounds that can be used include, but are not limited to, metal salts such as metal chlorides, metal nitrates, metal sulfates, and the like and combinations thereof.
- Metal-containing organic compounds can also be used. Examples of metal containing compounds useful in the present invention include, but are not limited to, zinc nitrate and dibutyltin bis(2-ethylhexanoate).
- An impregnating solution comprises a solution formed by dissolving a metal containing compound in a solvent such as water, alcohols, esters, ethers, ketones, hydrocarbons and combinations thereof.
- concentration of the metal in the solution can be in the range of from about 0.01 gram of metal per gram of solution to about 0.9 grams of metal promoter per gram of solution.
- the guard beds are generally arranged in a series containing from one to four separate guard beds.
- the guard beds can contain a compound selected from the group consisting of a molecular sieve, silica gel and combinations thereof.
- the molecular sieves are commonly either 3 Angstrom or 13 ⁇ molecular sieves.
- the guard beds can contain any combination of 3 Angstrom molecular sieves, silica gel, and 13 ⁇ molecular sieves.
- the guard beds can be regenerated by any suitable regeneration stream.
- the guard beds can be regenerated by contact with air or with a gaseous organic compound.
- the gaseous organic compound can be for example, gaseous isobutane.
- the guard bed regeneration process comprises, consists of, or consists essentially of the steps of: (a) contacting a regeneration stream with the guard bed to form an adsorbed stream, (b) condensing the adsorbed stream to form a condensed stream, (c) adding water to the condensed stream to form a waste stream, and (d) disposing of the waste stream.
- the zeolite catalyst can also be regenerated.
- the catalyst can be regenerated by any suitable regeneration stream.
- suitable regeneration streams include, but are not limited to, air, nitrogen, supercritical isobutane, and other light hydrocarbons.
- the regeneration conditions include a regeneration pressure in the range of from about 500 psi to about 1500 psi.
- the regeneration pressure can also be in the range of from about 529 psi to about 800 psi.
- the pressure can additionally be in the range of from 529 psi to 650 psi.
- the regeneration temperature depends on which regeneration stream is being used. Generally the temperature is in the range of from about 50° C. to about 900° C.
- the temperature when air is used, the temperature can be in the range of from about 250° C. to about 650° C., and additionally can be in the range of from 350° C. to 550° C.
- the temperature when nitrogen is used, the temperature can be in the range of from about 100° C. to about 500° C., and additionally can be in the range of from 200° C. to 400° C.
- the temperature when supercritical isobutane is used, the temperature can be in the range of from about 135° C. to about 500° C., and additionally can be in the range of from 135° C. to 300° C.
- the process of the first embodiment of the invention can also further comprise: (5) separating compounds comprising n-alkenes from the oligomerization product, (6) contacting the compounds comprising n-alkenes with an isomerization catalyst in an isomerization reaction zone under isomerization conditions to form an isomerization product; and (7) returning the isomerization product to the oligomerization zone.
- FIG. 1 further illustrates this embodiment of the invention.
- a hydrocarbon feed enters separator 22 via conduit 20 .
- separator 22 oligomers, such as for example either C4s or C5s are separated from the remainder of the feed.
- the remainder of the feed minus either the C4s or C5s, exits separator 22 via conduit 76 and passes on to further blending via conduit 78 .
- the separated C4 or C5 stream (referred to hereinafter as the “C4/C5 stream”) exits separator 22 via conduit 24 and passes through conduit 26 to guard bed 32 , which the C4/C5 stream enters via conduit 28 .
- Guard bed 32 contains compounds which can pretreat the C4/C5 stream before the C4/C5 stream enters the oligomerization zone.
- the C4/C5 stream leaves the guard bed via conduit 40 and then travels via conduit 48 to oligomerization reactor 60 , which the stream enters via conduit 56 .
- the C4/C5 stream is then oligomerized, and exits oligomerization reactor 60 via conduit 64 .
- the oligomerization product then travels via conduit 68 for the desired further processing.
- One option is to pass the oligomerization product to fractionator column 71 for further separation.
- the fractionated product then exits fractionator column 71 via conduits 72 and 74 , moving on to any desired further blending.
- guard bed 34 and reactor 62 go through a regeneration cycle.
- Regeneration fluid in conduit 50 passes into guard bed 34 via conduit 46 .
- the regeneration fluid removes the water that was collected in guard bed 34 and both the regeneration fluid and water exit guard bed 34 via conduit 38 and pass through cooler 54 and then to vessel 52 via conduit 81 .
- Vessel 52 separates the regeneration fluid from water and other impurities. Additional water can enter vessel 52 via opening 85 to help with this process.
- the water and other impurities exit vessel 52 via conduit 83 .
- the now separated regeneration fluid exits vessel 52 via conduit 50 , passes through pump 87 which raises the pressure, and continues via conduit 50 , is vaporized by heater 140 and then enters guard bed 34 via conduit 46 to begin the regeneration process once more.
- valves 104 , 108 , 114 , 118 , 122 , 126 , 128 and 132 are open while valves 106 , 110 , 112 , 116 , 120 , 124 , 130 and 134 are closed.
- the open valves can be closed and the closed valves can be opened, in order to enable guard bed 34 and reactor 62 to be in the process phase, while guard bed 32 and reactor 60 enter the regeneration phase.
- the C4/C5 stream enters guard bed 34 via conduit 30 , and exits via conduit 44 , and subsequently enters reactor 62 via conduit 58 and exits reactor 62 via conduit 66 .
- regeneration fluid enters guard bed 32 via conduit 42 and exits via conduits 28 and 36 .
- An air/nitrogen regeneration stream can enter reactor 60 via conduit 64 and exits via conduit 56 . The rest of the process continues to operate in the manner described above.
- Another embodiment of the invention is a process comprising, consisting of, or consisting essentially of the steps of:
- dehydrogenation conditions comprise a reaction temperature in the range of from about 150° C. to about 1000° C.
- the reaction temperature can also be in the range of from about 200° C. to about 650° C., and, additionally, the reaction temperature can be in the range of from about 300° C. to about 650° C.
- the dehydrogenation product comprises olefins having either 4 or 5 carbon atoms per molecule. These olefins are then oligomerized in an oligomerization zone under oligomerization reaction conditions.
- the oligomerization reaction conditions are the same as described above.
- the oligomerization catalyst used in this embodiment can be any catalyst that is used in the previous embodiment, as described above.
- the catalyst can also be pre-treated with a metal-containing compound, such as, for example, a zinc or tin-containing compound, as described above.
- the oligomerization process of step (2) produces a product comprised of oligomers and gasoline components. If the dehydrogenation product comprises C4s, then the oligomerization product comprises of compounds with 4, 8, and 12 or more carbon atoms per molecule. If the dehydrogenation product comprises C5s, then the oligomerization product comprises of compounds with 5, 10, and 15 or more carbon atoms per molecule. These different compounds are then separated via different separation zones. The compounds with 8 or 10 carbon atoms per molecule are then returned to an oligomerization zone, which can be the same oligomerization zone as in step (2) or a separate one. The compounds with 4 or 5 carbon atoms per molecule which comprise unreacted paraffins are returned to the dehydrogenation zone and the compounds with 12 or more carbon atoms per molecule are sent to a hydrotreating zone for the distillate pool.
- FIG. 2 further illustrates this embodiment of the invention.
- system 200 is illustrated in the following manner: a hydrocarbon stream enters dehydrogenation zone 212 via conduit 210 .
- the hydrocarbons are then dehydrogenated.
- Dehydrogenation zone 212 can be any suitable dehydrogenation system known in the art. This stream is dehydrogenated to form a mixture of normal butenes and isobutene. Hydrogen and lighter carbon molecules exit dehydrogenation zone 212 via conduit 214 .
- the dehydrogenation product comprising either C4s or C5s enters oligomerization zone 220 via conduit 216 .
- Other C4 or C5 olefins can join conduit 216 via conduit 218 and thereafter also enter oligomerization zone 220 .
- Oligomerization zone 220 is configured as the system disclosed in FIG. 1 above.
- the C4 or C5 olefins are oligomerized in oligomerization zone 220 to form olefins containing 8, 10 and 12 or more carbon atoms per molecule (in the case of a C4 feed) or olefins containing 5, 10, and 15 or more carbon atoms per molecule (in the case of a C5 feed).
- the resulting oligomerization product then passes into separation zone 224 via conduit 222 .
- separation zone 224 C8+ olefins are separated from C4 olefins or C10+ olefins are separated from C5 olefins.
- the C4 or C5 olefins leave the separation zone 224 via conduit 226 and are recycled back to the oligomerization zone via conduit 242 which will join conduit 216 to enter oligomerization zone 220 . Additionally, alkanes are separated in separation zone 224 . These compounds are recycled to the dehydrogenation zone via conduit 236 . This conduit joins conduit 210 leading into dehydrogenation zone 212 .
- the C8 or C10 olefins enter separation zone 230 via conduit 228 . In separation zone 230 , the C12+ compounds are separated from the C8 or C10 olefins.
- the C8 or C10 olefins exit separation zone 230 via conduit 232 and go on to further gasoline processing.
- the C12+ compounds exit separation zone 230 via conduit 234 and to then move on to further kerosene or diesel processing. Hydrogen can be added to conduit 234 via conduit 240 .
- Another embodiment of the invention is a process comprising, consisting of, or consisting essentially of the steps of:
- paraffins include, but are not limited to propane, isobutanes, isopentanes, and isohexanes.
- suitable internal olefins include, but are not limited to, isobutene, isopentenes, and isohexenes.
- suitable alpha olefins include, but are not limited to, propene, 1-butene, 1-pentene, and 1-hexene.
- a suitable feed is a feed comprising isopentane, isobutene, and 1-butene.
- the olefins are present in the feed in an amount in the range of from about 0.1 weight percent to about 100 weight percent based on the total weight of the feed.
- the alpha olefin can be present in an amount in the range of from about 5 weight percent to about 35 weight percent, and the alpha olefin can also be present in the range of from 10 weight percent to 25 weight percent, based on the total weight of the feed.
- the internal olefin can be present in an amount in the range of from about 5 weight percent to about 35 weight percent, and the internal olefin can also be present in the range of from 10 weight percent to about 25 weight percent based on the total weight of the feed.
- the catalyst used and the oligomerization reaction conditions in the oligomerization zone are the same as in the previous embodiments, as described above.
- Three different C5 feedstocks were oligomerized by the following process: a mordenite catalyst was placed into a cylindrical reactor tube. A feed was then passed from a feed pump to a series of two guard beds for treatment. The feed was then passed into the reactor tube, where it underwent oligomerization and was afterwards collected in a collection vessel. Table 1 below shows results for three C5 feeds, labeled as Feed 1, Feed 2, and Feed 3. Feed 2 has the highest sulfur content. Table 1 shows weight percent conversion after 4 days of oligomerization. For each feed there was a run with guard bed treatment and a run eliminating the guard bed treatment step.
- a C5 feedstock was oligomerized by the following process: a 26.25-gram quantity of an H-Mordenite 90 catalyst was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 ⁇ sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The guard beds were regenerated at 230° C. with dilute air and the catalyst was regenerated with dilute air at 550° C. The reaction system was run for 137.4 hours. The results are shown in Table II below.
- FIG. 3 shows the results of the regeneration of the mordenite with nitrogen and with supercritical isobutane.
- a C4 feedstock was oligomerized by the following process: 6.5 grams of H-Mordenite 40 catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 144.2 hours. The results are shown in Table III below.
- H-Mordenite 40 catalyst was treated with zinc nitrate.
- a 0.1 gram quantity of zinc nitrate hexahydrate was dissolved in 8 mL of water. The mixture was then heated to a temperature of 250° C to dissolve the zinc nitrate. This mixture was then added to 15 grams of a H-Mordenite 40 catalyst in 3 increments. The catalyst was then dried.
- the catalyst was then tested for oligomerization activity with a C4 feed by the following process: 6.5 grams of the catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 148 hours. The results are shown in Table IV below.
- H-Mordenite 40 catalyst was treated with dibutyltin bis(2-ethylhexanoate). A 0.25 gram quantity of dibutyltin bis(2-ethylhexanoate) was dissolved in 8 mL of acetone. This mixture was heated, and then added to 15 grams of a H-Mordenite 40 catalyst in 3 increments. The catalyst was then dried.
- the catalyst was then tested for oligomerization activity with a C4 feed by the following process: 6.5 grams of the catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145.5 hours. The results are shown in Table V below.
- a feed comprising 10% 1-butene in isopentane was oligomerized by the following process: 8 grams of an H-Mordenite 40 catalyst which was treated with zinc nitrate as described in Example IV was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 ⁇ sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145 hours. The results are shown in Table VI below.
- a feed comprising 10% 1-butene and 1% isobutene in isopentane was oligomerized by the following process: 8 grams of an H-Mordenite 40 catalyst which was treated with zinc nitrate as in Example V was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13 ⁇ sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145.8 hours. The results are shown in Table VII below.
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Abstract
Description
- The present invention relates generally to processing hydrocarbon-containing streams. In one aspect, the invention concerns processes for the oligomerization of hydrocarbon-containing streams.
- Much of the refinery related research over the past 5-10 years has been directed at converting light naphtha streams that are too high in Reid Vapor Pressure (RVP) for large volume use in gasoline, to higher molecular weight gasoline and diesel range compounds with lower RVP values. The desire for such capabilities continues to grow with downward pressure on gasoline RVP to reduce fugitive emissions into the atmosphere and as the use of ethanol in the gasoline pool increases.
- The Reid Vapor Pressure is a measure of the vapor pressure of gasoline, volatile crude oils, and other volatile petroleum products determined at approximately 38° C. In the past decades, the Environmental Protection Agency (EPA) imposed regulations controlling hydrocarbon emissions from fuel sources in order to reduce ground ozone levels. Volatile organic compounds (VOCs) from evaporative sources are a major source for the generation of this urban ozone. Thus, restrictions on light hydrocarbon streams become more and more stringent forcing the lightest components out of the available fuel pool. With increased ethanol blending, this problem will be exacerbated since blending ethanol requires a lower RVP base stock to achieve overall final fuel RVP specifications.
- In 2012, about four hundred ninety thousand barrels per day of renewable fuels (mainly comprising ethanol) will be mandated. The use of ethanol in reformulated gasoline (RFG) will not be optional for many refiners as they will need to use it to achieve octane. If by 2012 all the gasoline pool is mandated to be RFG then the displaced C5 would further double assuming the required volume of renewables remains constant. In addition, these objectives must be met without negatively impacting other fuel parameters such as octane and distillation points.
- In accordance with the present invention, a process has been discovered which comprises, consists of, or consists essentially of
-
- (1) separating a hydrocarbon stream in a separation zone to provide a separated product comprising olefins;
- (2) contacting the olefins with at least one guard bed to provide pretreated olefins,
- (3) contacting the pretreated olefins with a catalyst comprising a zeolite in an oligomerization zone under oligomerization reaction conditions to form an oligomerization product; and
- (4) recovering the oligomerization product.
- Another embodiment of the invention is a process which comprises, consists of, or consists essentially of:
-
- (1) dehydrogenating a hydrocarbon feedstock comprising paraffins in a dehydrogenation zone under dehydrogenation conditions to form a dehydrogenation product comprising olefins;
- (2) oligomerizing the olefins in an oligomerization reaction zone under oligomerization reaction conditions to form an oligomerization product comprising of oligomers and gasoline;
- (3) separating a first component comprising compounds selected from the group consisting of compounds with 8 carbon atoms per molecule and compounds with 10 carbon atoms per molecule from the oligomerization product in a first separation zone;
- (4) returning said first component to an oligomerization reaction zone;
- (5) separating a second component comprising compounds selected from the group consisting of compounds with 4 carbon atoms per molecule and compounds with 5 carbon atoms per molecule from the oligomerization product in a second separation zone;
- (6) returning the second component to said dehydrogenation zone;
- (7) separating a third component comprising compounds with at least 12 carbon atoms per molecule from the oligomerization product in a third separation zone; and
- (8) transferring the third component to a hydrotreating zone.
- Still another embodiment of the invention is a process which comprises, consists of, or consists essentially of:
-
- (1) contacting a feed comprising, consisting of, or consisting essentially of a paraffin, an internal olefin and an alpha olefin with an oligomerization catalyst in a oligomerization reaction zone under oligomerization reaction conditions to provide an oligomerization product; and
- (2) recovering said oligomerization product.
- Other objects and advantages will become apparent from the detailed description and the appended claims.
-
FIG. 1 depicts an oligomerization process system. -
FIG. 2 depicts a hydrocarbon processing and separation system. -
FIG. 3 is a graph plotting the weight percent of olefin conversion vs. time on-stream. - One embodiment of the present invention is a process comprising, consisting of, or consisting essentially of:
-
- (1) separating a hydrocarbon stream in a separation zone to provide a separated product comprising olefins;
- (2) contacting said olefins with at least one guard bed to provide pretreated olefins,
- (3) contacting said pretreated olefins with a catalyst comprising a zeolite in an oligomerization zone under oligomerization reaction conditions to form an oligomerization product; and
- (4) recovering the oligomerization product.
- Any zeolite-containing catalyst which is effective for the oligomerization of hydrocarbons can be used. Generally, the molar ratio of SiO2 to Al2O3 in the crystalline framework of the zeolite is in the range of from about 10:1 to about 150:1. The molar ratio of SiO2 to Al2O3 in the zeolite framework can also be in the range of from about 30:1 to about 100:1. Examples of zeolites that can be used include, but are not limited to mordenites. Examples of mordenites that can be used include but are not limited to Mordenite 40, Mordenite 90 and their hydrogen-promoted counterparts.
- Any olefin can be oligomerized by the process of the present invention. Generally, the olefins have in the range of from 2 to 20 carbon atoms per molecule. The olefins can also have in the range of from 3 to 6 carbon atoms per molecule, and, additionally, the olefins can have 4 to 5 carbon atoms per molecule.
- Generally, the oligomerization reaction conditions in the oligomerization reaction zone include a temperature in the range of from about 35° C. to about 260° C. The temperature can also be in the range of from about 65° C. to about 150° C., and, additionally, the temperature can be in the range of from 90° C. to 130° C.
- The oligomerization reaction conditions also include a pressure in the range of from about 100 psi to about 800 psi. The pressure can also be in the range of from about 300 psi to about 500 psi, and, additionally, the pressure can range from 200 psi to 600 psi. The desired pressure maintains the process stream in the liquid form.
- Before contacting the zeolite catalyst with olefins in an oligomerization zone, the zeolite can optionally be treated with one or more metal compounds in order to increase the acidity of the zeolite. The zeolite can be treated with compounds containing metals selected from the group consisting of zinc, cadmium, copper, silver, gold, gallium, indium, silicon, germanium, and tin. Generally, the compound contains zinc or tin. The metal compound can be incorporated into or onto the zeolite. One method of incorporating is to impregnate using any standard incipient wetness impregnation technique (i.e. essentially completely or partially filling the pores of a substrate material with a solution of the incorporating elements) for impregnating a substrate. This method uses an impregnating solution comprising the desirable concentration of a metal containing compound. Metal containing compounds that can be used include, but are not limited to, metal salts such as metal chlorides, metal nitrates, metal sulfates, and the like and combinations thereof. Metal-containing organic compounds can also be used. Examples of metal containing compounds useful in the present invention include, but are not limited to, zinc nitrate and dibutyltin bis(2-ethylhexanoate). An impregnating solution comprises a solution formed by dissolving a metal containing compound in a solvent such as water, alcohols, esters, ethers, ketones, hydrocarbons and combinations thereof. The concentration of the metal in the solution can be in the range of from about 0.01 gram of metal per gram of solution to about 0.9 grams of metal promoter per gram of solution.
- In order to reduce potential catalyst poisons, it is desirable to pass the olefins through a series of one or more guard beds before the olefins are contacted with a zeolite catalyst. The guard beds are generally arranged in a series containing from one to four separate guard beds. The guard beds can contain a compound selected from the group consisting of a molecular sieve, silica gel and combinations thereof. The molecular sieves are commonly either 3 Angstrom or 13× molecular sieves. The guard beds can contain any combination of 3 Angstrom molecular sieves, silica gel, and 13× molecular sieves. The guard beds can be regenerated by any suitable regeneration stream. The guard beds can be regenerated by contact with air or with a gaseous organic compound. The gaseous organic compound can be for example, gaseous isobutane. The guard bed regeneration process comprises, consists of, or consists essentially of the steps of: (a) contacting a regeneration stream with the guard bed to form an adsorbed stream, (b) condensing the adsorbed stream to form a condensed stream, (c) adding water to the condensed stream to form a waste stream, and (d) disposing of the waste stream.
- The zeolite catalyst can also be regenerated. The catalyst can be regenerated by any suitable regeneration stream. Examples of suitable regeneration streams include, but are not limited to, air, nitrogen, supercritical isobutane, and other light hydrocarbons. Generally the regeneration conditions include a regeneration pressure in the range of from about 500 psi to about 1500 psi. The regeneration pressure can also be in the range of from about 529 psi to about 800 psi. The pressure can additionally be in the range of from 529 psi to 650 psi. The regeneration temperature depends on which regeneration stream is being used. Generally the temperature is in the range of from about 50° C. to about 900° C. For example, when air is used, the temperature can be in the range of from about 250° C. to about 650° C., and additionally can be in the range of from 350° C. to 550° C. When nitrogen is used, the temperature can be in the range of from about 100° C. to about 500° C., and additionally can be in the range of from 200° C. to 400° C. When supercritical isobutane is used, the temperature can be in the range of from about 135° C. to about 500° C., and additionally can be in the range of from 135° C. to 300° C.
- The process of the first embodiment of the invention can also further comprise: (5) separating compounds comprising n-alkenes from the oligomerization product, (6) contacting the compounds comprising n-alkenes with an isomerization catalyst in an isomerization reaction zone under isomerization conditions to form an isomerization product; and (7) returning the isomerization product to the oligomerization zone.
-
FIG. 1 further illustrates this embodiment of the invention. - Referring to
FIG. 1 ,system 10 is illustrated in the following manner: a hydrocarbon feed entersseparator 22 viaconduit 20. Inseparator 22, oligomers, such as for example either C4s or C5s are separated from the remainder of the feed. The remainder of the feed, minus either the C4s or C5s, exitsseparator 22 viaconduit 76 and passes on to further blending viaconduit 78. Meanwhile, the separated C4 or C5 stream (referred to hereinafter as the “C4/C5 stream”) exitsseparator 22 viaconduit 24 and passes throughconduit 26 to guardbed 32, which the C4/C5 stream enters viaconduit 28.Guard bed 32 contains compounds which can pretreat the C4/C5 stream before the C4/C5 stream enters the oligomerization zone. The C4/C5 stream leaves the guard bed viaconduit 40 and then travels viaconduit 48 tooligomerization reactor 60, which the stream enters viaconduit 56. The C4/C5 stream is then oligomerized, and exitsoligomerization reactor 60 viaconduit 64. The oligomerization product then travels viaconduit 68 for the desired further processing. One option is to pass the oligomerization product tofractionator column 71 for further separation. The fractionated product then exitsfractionator column 71 viaconduits - Meanwhile,
guard bed 34 andreactor 62 go through a regeneration cycle. Regeneration fluid inconduit 50 passes intoguard bed 34 viaconduit 46. The regeneration fluid removes the water that was collected inguard bed 34 and both the regeneration fluid and waterexit guard bed 34 viaconduit 38 and pass through cooler 54 and then tovessel 52 viaconduit 81.Vessel 52 separates the regeneration fluid from water and other impurities. Additional water can entervessel 52 via opening 85 to help with this process. The water and other impurities exitvessel 52 viaconduit 83. The now separated regeneration fluid exitsvessel 52 viaconduit 50, passes throughpump 87 which raises the pressure, and continues viaconduit 50, is vaporized byheater 140 and then entersguard bed 34 viaconduit 46 to begin the regeneration process once more. - While
reactor 60 is active,reactor 62 is in the regeneration phase. Air entersair compressor 86 viaconduit 84. The air then travels viaconduit 88, mixes with recycle gas inconduit 90, then joins a nitrogen stream inconduit 80. The air/nitrogen stream then travels toconduit 70 and entersreactor 62 viaconduit 66. The stream exitsreactor 62 viaconduit 58 and travels viaconduit 92 to coolingunit 94, then tovessel 96, where condensed water is knocked out of the stream, exitingvessel 96 throughconduit 98. Inert gases leavevessel 96 viaconduit 100. Some off gases are purged, while regenerator off-gas passes throughrecycle compressor 102 and back toconduit 90. In this process,valves valves guard bed 34 andreactor 62 to be in the process phase, whileguard bed 32 andreactor 60 enter the regeneration phase. In this process, the C4/C5 stream entersguard bed 34 viaconduit 30, and exits viaconduit 44, and subsequently entersreactor 62 viaconduit 58 and exitsreactor 62 viaconduit 66. Meanwhile, regeneration fluid entersguard bed 32 viaconduit 42 and exits viaconduits reactor 60 viaconduit 64 and exits viaconduit 56. The rest of the process continues to operate in the manner described above. - Another embodiment of the invention is a process comprising, consisting of, or consisting essentially of the steps of:
-
- (1) dehydrogenating a hydrocarbon feedstock comprising paraffins in a dehydrogenation zone under dehydrogenation conditions to form a dehydrogenation product comprising olefins;
- (2) oligomerizing said olefins in an oligomerization reaction zone under oligomerization reaction conditions to form an oligomerization product comprising of oligomers and gasoline components;
- (3) separating a first component comprising compounds selected from the group consisting of compounds with 8 carbon atoms per molecule and compounds with 10 carbon atoms per molecule from the oligomerization product in a first separation zone;
- (4) returning said first component to an oligomerization reaction zone;
- (5) separating a second component comprising compounds selected from the group consisting of compounds with 4 carbon atoms per molecule and compounds with 5 carbon atoms per molecule from the oligomerization product in a second separation zone;
- (6) returning the second component to the dehydrogenation zone;
- (7) separating a third component comprising compounds with at least 12 carbon atoms per molecule from the oligomerization product in a third separation zone; and
- (8) transferring the third component to a hydrotreating zone. The gasoline components can also be separated from the oligomerization product so it can be put to further use.
- Generally, dehydrogenation conditions comprise a reaction temperature in the range of from about 150° C. to about 1000° C. The reaction temperature can also be in the range of from about 200° C. to about 650° C., and, additionally, the reaction temperature can be in the range of from about 300° C. to about 650° C.
- The dehydrogenation product comprises olefins having either 4 or 5 carbon atoms per molecule. These olefins are then oligomerized in an oligomerization zone under oligomerization reaction conditions.
- The oligomerization reaction conditions are the same as described above.
- The oligomerization catalyst used in this embodiment can be any catalyst that is used in the previous embodiment, as described above. The catalyst can also be pre-treated with a metal-containing compound, such as, for example, a zinc or tin-containing compound, as described above.
- The oligomerization process of step (2) produces a product comprised of oligomers and gasoline components. If the dehydrogenation product comprises C4s, then the oligomerization product comprises of compounds with 4, 8, and 12 or more carbon atoms per molecule. If the dehydrogenation product comprises C5s, then the oligomerization product comprises of compounds with 5, 10, and 15 or more carbon atoms per molecule. These different compounds are then separated via different separation zones. The compounds with 8 or 10 carbon atoms per molecule are then returned to an oligomerization zone, which can be the same oligomerization zone as in step (2) or a separate one. The compounds with 4 or 5 carbon atoms per molecule which comprise unreacted paraffins are returned to the dehydrogenation zone and the compounds with 12 or more carbon atoms per molecule are sent to a hydrotreating zone for the distillate pool.
-
FIG. 2 further illustrates this embodiment of the invention. - Referring to
FIG. 2 ,system 200 is illustrated in the following manner: a hydrocarbon stream entersdehydrogenation zone 212 viaconduit 210. The hydrocarbons are then dehydrogenated.Dehydrogenation zone 212 can be any suitable dehydrogenation system known in the art. This stream is dehydrogenated to form a mixture of normal butenes and isobutene. Hydrogen and lighter carbon moleculesexit dehydrogenation zone 212 viaconduit 214. Meanwhile, the dehydrogenation product comprising either C4s or C5s entersoligomerization zone 220 viaconduit 216. Other C4 or C5 olefins can joinconduit 216 viaconduit 218 and thereafter also enteroligomerization zone 220.Oligomerization zone 220 is configured as the system disclosed inFIG. 1 above. The C4 or C5 olefins are oligomerized inoligomerization zone 220 to form olefins containing 8, 10 and 12 or more carbon atoms per molecule (in the case of a C4 feed) or olefins containing 5, 10, and 15 or more carbon atoms per molecule (in the case of a C5 feed). The resulting oligomerization product then passes intoseparation zone 224 viaconduit 222. Inseparation zone 224, C8+ olefins are separated from C4 olefins or C10+ olefins are separated from C5 olefins. The C4 or C5 olefins leave theseparation zone 224 viaconduit 226 and are recycled back to the oligomerization zone viaconduit 242 which will joinconduit 216 to enteroligomerization zone 220. Additionally, alkanes are separated inseparation zone 224. These compounds are recycled to the dehydrogenation zone viaconduit 236. This conduit joinsconduit 210 leading intodehydrogenation zone 212. The C8 or C10 olefins enterseparation zone 230 viaconduit 228. Inseparation zone 230, the C12+ compounds are separated from the C8 or C10 olefins. The C8 or C10 olefins exitseparation zone 230 viaconduit 232 and go on to further gasoline processing. The C12+ compoundsexit separation zone 230 viaconduit 234 and to then move on to further kerosene or diesel processing. Hydrogen can be added toconduit 234 viaconduit 240. - Another embodiment of the invention is a process comprising, consisting of, or consisting essentially of the steps of:
-
- (1) contacting a feed comprising a paraffin, an internal olefin and an alpha olefin with an oligomerization catalyst in a oligomerization reaction zone under oligomerization reaction conditions to provide an oligomerization product; and
- (2) recovering the oligomerization product.
- Any suitable paraffin, internal olefin and alpha olefin can be used. Examples of suitable paraffins include, but are not limited to propane, isobutanes, isopentanes, and isohexanes. Examples of suitable internal olefins include, but are not limited to, isobutene, isopentenes, and isohexenes. Examples of suitable alpha olefins include, but are not limited to, propene, 1-butene, 1-pentene, and 1-hexene. One example of a suitable feed is a feed comprising isopentane, isobutene, and 1-butene.
- Generally, the olefins are present in the feed in an amount in the range of from about 0.1 weight percent to about 100 weight percent based on the total weight of the feed. The alpha olefin can be present in an amount in the range of from about 5 weight percent to about 35 weight percent, and the alpha olefin can also be present in the range of from 10 weight percent to 25 weight percent, based on the total weight of the feed. The internal olefin can be present in an amount in the range of from about 5 weight percent to about 35 weight percent, and the internal olefin can also be present in the range of from 10 weight percent to about 25 weight percent based on the total weight of the feed.
- The catalyst used and the oligomerization reaction conditions in the oligomerization zone are the same as in the previous embodiments, as described above.
- The following examples are presented to further illustrate this invention and are not to be construed as unduly limiting its scope.
- Three different C5 feedstocks were oligomerized by the following process: a mordenite catalyst was placed into a cylindrical reactor tube. A feed was then passed from a feed pump to a series of two guard beds for treatment. The feed was then passed into the reactor tube, where it underwent oligomerization and was afterwards collected in a collection vessel. Table 1 below shows results for three C5 feeds, labeled as Feed 1, Feed 2, and Feed 3. Feed 2 has the highest sulfur content. Table 1 shows weight percent conversion after 4 days of oligomerization. For each feed there was a run with guard bed treatment and a run eliminating the guard bed treatment step.
-
TABLE I FEED 1 FEED 2 FEED 3 Source Feed Product Feed Product Feed Product Dienes, ppmw 0.2 NA 1.1 NA <0.1 NA Sulfur, ppmw 2.3 2.8 33 27 1.4 0.0 Nitrogen, ppmw 1.0 <0.1 1.0 0.1 0.1 <0.1 Conversion, 48 19 62 wt. % 4 days w/o guard beds Conversion, 61 13 62 wt. % 4 days w/o guard beds - A C5 feedstock was oligomerized by the following process: a 26.25-gram quantity of an H-
Mordenite 90 catalyst was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Å sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The guard beds were regenerated at 230° C. with dilute air and the catalyst was regenerated with dilute air at 550° C. The reaction system was run for 137.4 hours. The results are shown in Table II below. -
TABLE II Time on Stream, hrs. Net Conversion (wt. %) 1.8 60 10.7 62 18.9 65 29.5 65 42.4 66 78.3 62 113.7 61 125.7 60 137.4 63 - A C5 feedstock was oligomerized by the process of Example II.
FIG. 3 shows the results of the regeneration of the mordenite with nitrogen and with supercritical isobutane. - A C4 feedstock was oligomerized by the following process: 6.5 grams of H-
Mordenite 40 catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 144.2 hours. The results are shown in Table III below. -
TABLE III Time on-stream, hrs. Conversion (wt. %) Selectivity to C8's (wt. %) 6 99.79 19.96 16.5 99.36 27.72 23.8 91.40 40.04 30.3 49.04 60.15 40.4 9.55 77.70 64.3 −0.74 90.57 88.3 −3.50 100.00 95.9 −0.96 91.18 102.1 3.82 82.61 112.2 21.13 92.02 121.7 80.04 72.36 125.8 90.02 69.40 136.1 96.18 58.33 144.2 97.88 50.77
Inventive (Catalyst Treated with Zinc) - An H-
Mordenite 40 catalyst was treated with zinc nitrate. A 0.1 gram quantity of zinc nitrate hexahydrate was dissolved in 8 mL of water. The mixture was then heated to a temperature of 250° C to dissolve the zinc nitrate. This mixture was then added to 15 grams of a H-Mordenite 40 catalyst in 3 increments. The catalyst was then dried. - The catalyst was then tested for oligomerization activity with a C4 feed by the following process: 6.5 grams of the catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 148 hours. The results are shown in Table IV below.
-
TABLE IV Time on-stream, hrs. Conversion (wt. %) Selectivity to C8's (wt. %) 4.7 99.90 17.64 14.6 99.90 23.5 21.9 99.80 24.33 28.6 99.70 24.85 29.6 98.88 30.82 46.3 96.14 39.27 52.3 90.35 47.23 62.6 71.44 61.80 71.4 50.51 76.51 76.4 37.60 82.61 93.5 23.88 91.94 114.5 23.07 93.05 134.3 37.70 88.37 141.9 43.29 89.02 148 52.64 86.07
Inventive (Catalyst Treated with Tin) - An H-
Mordenite 40 catalyst was treated with dibutyltin bis(2-ethylhexanoate). A 0.25 gram quantity of dibutyltin bis(2-ethylhexanoate) was dissolved in 8 mL of acetone. This mixture was heated, and then added to 15 grams of a H-Mordenite 40 catalyst in 3 increments. The catalyst was then dried. - The catalyst was then tested for oligomerization activity with a C4 feed by the following process: 6.5 grams of the catalyst, diluted with a 30 mL volume of 14 grit alundum was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145.5 hours. The results are shown in Table V below.
-
TABLE V Time on-stream, hrs. Conversion (wt. %) Selectivity to C8's (wt. %) 6.8 99.90 21.60 17.3 99.69 26.49 24.9 99.38 29.64 30.8 97.83 35.31 64.7 38.60 72.38 97.8 5.78 83.91 102.9 7.12 73.02 113.4 39.22 87.65 120.9 85.45 69.17 127 92.16 65.89 137.5 94.84 62.97 145.5 96.49 58.91 - I. Control
- A feed comprising 10% 1-butene in isopentane was oligomerized by the following process: 8 grams of an H-
Mordenite 40 catalyst which was treated with zinc nitrate as described in Example IV was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Å sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145 hours. The results are shown in Table VI below. -
TABLE VI Time on-stream, Conversion Selectivity to Selectivity to Selectivity to hrs. (wt. %) C8's (wt. %) C12's (wt. %) C16's (wt. %) 5.6 84.76 58.66 31.00 10.33 16.4 82.41 64.81 27.22 7.97 23.9 81.49 64.11 26.00 9.90 29.6 80.78 64.02 26.01 9.97 95.9 76.28 72.34 24.54 3.11 98.2 67.69 70.75 23.44 5.81 102.4 67.28 67.16 25.68 7.16 118.6 88.75 53.82 31.22 14.96 126.6 88.24 48.34 28.14 23.52 142.6 88.24 53.25 28.39 18.37 145 92.02 43.66 27.58 28.76 - II. Inventive
- A feed comprising 10% 1-butene and 1% isobutene in isopentane was oligomerized by the following process: 8 grams of an H-
Mordenite 40 catalyst which was treated with zinc nitrate as in Example V was placed into a cylindrical reactor tube. The feed was then passed from a feed pump to a series of two guard beds, which contained a 3 Angstrom sieve, silica gel, and a 13× sieve. The feed then passed into the reactor tube, where it then underwent oligomerization and was afterwards collected in a collection vessel. The reaction system ran for about 145.8 hours. The results are shown in Table VII below. -
TABLE VII Time on-stream, Conversion Selectivity to Selectivity to Selectivity to hrs. (wt. %) C8's (wt. %) C12's (wt. %) C16's (wt. %) 6.8 87.38 42.91 30.76 26.33 17.6 94.54 43.29 27.14 29.57 24.6 95.76 44.30 30.01 25.69 31.2 96.99 39.90 29.34 30.76 41.6 98.12 39.93 32.21 27.86 48.9 98.87 36.10 30.35 33.55 55 99.34 35.91 30.43 33.66 65.9 99.25 37.88 32.52 29.60 73.8 99.06 35.50 29.20 35.29 78.8 98.87 39.42 31.09 29.49 113.3 98.31 45.09 31.55 23.35 145.8 98.21 37.56 27.67 34.77 - Reasonable variations, modifications, and adaptations may be made within the scope of this disclosure and the appended claims without departing from the scope of this invention.
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GB1008649.4A GB2467689B (en) | 2007-12-06 | 2008-11-21 | Oligomerization of hydrocarbons |
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MX2010006190A MX2010006190A (en) | 2007-12-06 | 2008-11-21 | Oligomerization of hydrocarbons. |
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US20150157998A1 (en) * | 2013-12-05 | 2015-06-11 | Uop Llc | Apparatus for the integration of dehydrogenation and oligomerization |
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Citations (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3291855A (en) * | 1965-12-30 | 1966-12-13 | Universal Oil Prod Co | Catalytic dehydrogenation of paraffinic hydrocarbons |
US3960978A (en) * | 1974-09-05 | 1976-06-01 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4021502A (en) * | 1975-02-24 | 1977-05-03 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4024203A (en) * | 1969-11-24 | 1977-05-17 | Institut Francais Du Petrole | Oligomerization of unsaturated hydrocarbons with acid catalysts |
US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
US4188501A (en) * | 1978-08-25 | 1980-02-12 | Phillips Petroleum Company | Purification of monoolefin-containing hydrocarbon stream |
US4268700A (en) * | 1978-09-28 | 1981-05-19 | Institut Francais Du Petrole | Process for producing gasoline of high octane number and particularly lead free gasoline, from olefininc C3 -C4 cuts |
US4293728A (en) * | 1980-03-31 | 1981-10-06 | Phillips Petroleum Co. | Pretreatment of butene-1 in isomerization of it to butene-2 |
US4377393A (en) * | 1979-11-03 | 1983-03-22 | Ec Erdolchemie Gmbh | Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture |
US4413153A (en) * | 1982-10-22 | 1983-11-01 | Mobil Oil Corporation | Integrated process for making transportation fuels and lubes from wet natural gas |
US4414423A (en) * | 1981-09-25 | 1983-11-08 | Chevron Research Company | Multistep oligomerization process |
US4423269A (en) * | 1981-09-25 | 1983-12-27 | Chevron Research Company | Oligomerization of gaseous olefins |
US4454367A (en) * | 1982-03-23 | 1984-06-12 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for the low polymerization of isobutene |
US4456779A (en) * | 1983-04-26 | 1984-06-26 | Mobil Oil Corporation | Catalytic conversion of olefins to higher hydrocarbons |
US4542247A (en) * | 1984-09-14 | 1985-09-17 | Mobil Oil Corporation | Conversion of LPG hydrocarbons to distillate fuels or lubes using integration of LPG dehydrogenation and MOGDL |
US4636225A (en) * | 1984-03-23 | 1987-01-13 | Linde Aktiengesellschaft | Drying of gases with multi-layer adsorption beds |
US4675461A (en) * | 1983-06-29 | 1987-06-23 | Mobil Oil Corporation | Conversion of LPG hydrocarbons into distillate fuels using an integral LPG dehydrogenation-MOGD process |
US4727203A (en) * | 1987-04-13 | 1988-02-23 | Shell Oil Company | Terminal to interior double bond isomerization process for an olefinic molecule with reduced dimerization |
US4749820A (en) * | 1984-09-14 | 1988-06-07 | Mobil Oil Corporation | Integration of paraffin dehydrogenation with MOGD to minimize compression and gas plant separation |
US4777316A (en) * | 1987-11-10 | 1988-10-11 | Mobil Oil Corporation | Manufacture of distillate hydrocarbons from light olefins in staged reactors |
US4788366A (en) * | 1987-12-28 | 1988-11-29 | Mobil Oil Corporation | Production of heavier hydrocarbons from light olefins in multistage catalytic reactors |
US4902847A (en) * | 1987-09-17 | 1990-02-20 | Institut Francais Du Petrole | Method for producing olefin oligomers using a modified mordenite based catalyst |
US4925995A (en) * | 1988-03-21 | 1990-05-15 | Shell Oil Company | Process for preparing liquid hydrocarbons |
US4939314A (en) * | 1988-12-19 | 1990-07-03 | Mobil Oil Corporation | Method for on-stream low-pressure regeneration of an oligomerization catalyst from a fluid-bed reactor operating at high pressure with hydrocarbons in a non-liquid phase |
US4971606A (en) * | 1989-11-06 | 1990-11-20 | Air Products And Chemicals, Inc. | Closed-loop thermal regeneration of adsorbents containing reactive adsorbates |
US4973790A (en) * | 1989-11-16 | 1990-11-27 | Mobil Oil Corporation | Process for upgrading light olefinic streams |
US5019357A (en) * | 1987-11-10 | 1991-05-28 | Mobil Oil Corporation | Reactor system for upgrading light olefins in staged reactors |
US5043517A (en) * | 1989-10-30 | 1991-08-27 | Mobil Oil Corporation | Upgrading light olefin fuel gas in a fluidized bed catalyst reactor and regeneration of the catalyst |
US5053579A (en) * | 1989-11-16 | 1991-10-01 | Mobil Oil Corporation | Process for upgrading unstable naphthas |
US5057640A (en) * | 1991-01-02 | 1991-10-15 | Mobil Oil Corp. | Propylene oligomerization over silica modified zeolites |
US5177282A (en) * | 1989-05-05 | 1993-01-05 | Huels Aktiengesellschaft | Oligomerization of olefins |
US5198099A (en) * | 1991-08-12 | 1993-03-30 | Exxon Research And Engineering Company | Three-stage process for producing ultra-clean distillate products |
US5234873A (en) * | 1989-03-03 | 1993-08-10 | Institut Francais Du Petrole | Catalyst with a mordenite base containing at least one metal of groups iia, ivb, iib or iva and its use in isomerization of a c8 aromatic cut |
US5405814A (en) * | 1990-07-25 | 1995-04-11 | Mobil Oil Corporation | Olefin conversion catalyst regeneration |
US5430220A (en) * | 1993-05-03 | 1995-07-04 | Phillips Petroleum Company | Platinum and tin-containing catalyst and use thereof in alkane dehydrogenation |
US5624547A (en) * | 1993-09-20 | 1997-04-29 | Texaco Inc. | Process for pretreatment of hydrocarbon oil prior to hydrocracking and fluid catalytic cracking |
US5672800A (en) * | 1992-01-30 | 1997-09-30 | Exxon Chemical Patents Inc. | Alkene oligomerization |
US5847252A (en) * | 1995-12-15 | 1998-12-08 | Uop Llc | Process for integrated oligomer production and saturation |
US5873994A (en) * | 1997-07-15 | 1999-02-23 | Phillips Petroleum Company | Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin |
US6281401B1 (en) * | 1999-09-16 | 2001-08-28 | Phillips Petroleum Company | Oligomerization of olefins |
US6500999B2 (en) * | 2000-05-26 | 2002-12-31 | Snamprogetti S.P.A. | Process for the production of hydrocarbons with a high octane number by means of the selective dimerization of isobutene with acid catalysts |
US6864398B2 (en) * | 2000-04-03 | 2005-03-08 | Chevron U.S.A. Inc. | Conversion of syngas to distillate fuels |
US6884914B2 (en) * | 2001-02-01 | 2005-04-26 | Exxon Mobil Chemical Patents Inc. | Olefin oligomerization |
US20080029437A1 (en) * | 2006-08-02 | 2008-02-07 | Exxonmobil Research And Engineering Company | Olefin upgrading process with guard bed regeneration |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4749819A (en) * | 1987-03-27 | 1988-06-07 | Shell Oil Company | Terminal to interior double bond isomerization process for an olefinic molecule |
US5026933A (en) * | 1987-10-07 | 1991-06-25 | Mobil Oil Corporation | Olefin oligomerization with surface modified zeolite catalyst |
US5024679A (en) * | 1987-12-08 | 1991-06-18 | Mobil Oil Corporation | Olefins etherification and conversion to liquid fuels with paraffins dehydrogenation |
NO995923L (en) | 1999-12-03 | 2001-06-05 | Norsk Hydro As | Submerged pipeline for transporting fluids such as oil and / or gas |
US7214846B2 (en) * | 2003-08-06 | 2007-05-08 | Exxonmobil Chemical Patents Inc. | Recovery of ethylene and propylene from a methanol to olefin reaction system |
US8481796B2 (en) * | 2005-01-31 | 2013-07-09 | Exxonmobil Chemical Patents Inc. | Olefin oligomerization and compositions therefrom |
-
2007
- 2007-12-06 US US11/951,863 patent/US7956227B2/en active Active
-
2008
- 2008-11-21 WO PCT/US2008/084286 patent/WO2009073395A1/en active Application Filing
- 2008-11-21 CA CA2707028A patent/CA2707028C/en active Active
- 2008-11-21 GB GB1008649.4A patent/GB2467689B/en active Active
- 2008-11-21 MX MX2010006190A patent/MX2010006190A/en active IP Right Grant
Patent Citations (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3291855A (en) * | 1965-12-30 | 1966-12-13 | Universal Oil Prod Co | Catalytic dehydrogenation of paraffinic hydrocarbons |
US4024203A (en) * | 1969-11-24 | 1977-05-17 | Institut Francais Du Petrole | Oligomerization of unsaturated hydrocarbons with acid catalysts |
US3960978A (en) * | 1974-09-05 | 1976-06-01 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4021502A (en) * | 1975-02-24 | 1977-05-03 | Mobil Oil Corporation | Converting low molecular weight olefins over zeolites |
US4150062A (en) * | 1976-12-20 | 1979-04-17 | Mobil Oil Corporation | Light olefin processing |
US4188501A (en) * | 1978-08-25 | 1980-02-12 | Phillips Petroleum Company | Purification of monoolefin-containing hydrocarbon stream |
US4268700A (en) * | 1978-09-28 | 1981-05-19 | Institut Francais Du Petrole | Process for producing gasoline of high octane number and particularly lead free gasoline, from olefininc C3 -C4 cuts |
US4377393A (en) * | 1979-11-03 | 1983-03-22 | Ec Erdolchemie Gmbh | Process for the preparation of a mixture consisting essentially of iso-butene oligomers and methyl tert.-butyl ether, its use, and fuels containing such mixture |
US4293728A (en) * | 1980-03-31 | 1981-10-06 | Phillips Petroleum Co. | Pretreatment of butene-1 in isomerization of it to butene-2 |
US4414423A (en) * | 1981-09-25 | 1983-11-08 | Chevron Research Company | Multistep oligomerization process |
US4423269A (en) * | 1981-09-25 | 1983-12-27 | Chevron Research Company | Oligomerization of gaseous olefins |
US4454367A (en) * | 1982-03-23 | 1984-06-12 | Toa Nenryo Kogyo Kabushiki Kaisha | Process for the low polymerization of isobutene |
US4413153A (en) * | 1982-10-22 | 1983-11-01 | Mobil Oil Corporation | Integrated process for making transportation fuels and lubes from wet natural gas |
US4456779A (en) * | 1983-04-26 | 1984-06-26 | Mobil Oil Corporation | Catalytic conversion of olefins to higher hydrocarbons |
US4675461A (en) * | 1983-06-29 | 1987-06-23 | Mobil Oil Corporation | Conversion of LPG hydrocarbons into distillate fuels using an integral LPG dehydrogenation-MOGD process |
US4636225A (en) * | 1984-03-23 | 1987-01-13 | Linde Aktiengesellschaft | Drying of gases with multi-layer adsorption beds |
US4749820A (en) * | 1984-09-14 | 1988-06-07 | Mobil Oil Corporation | Integration of paraffin dehydrogenation with MOGD to minimize compression and gas plant separation |
US4542247A (en) * | 1984-09-14 | 1985-09-17 | Mobil Oil Corporation | Conversion of LPG hydrocarbons to distillate fuels or lubes using integration of LPG dehydrogenation and MOGDL |
US4727203A (en) * | 1987-04-13 | 1988-02-23 | Shell Oil Company | Terminal to interior double bond isomerization process for an olefinic molecule with reduced dimerization |
US4902847A (en) * | 1987-09-17 | 1990-02-20 | Institut Francais Du Petrole | Method for producing olefin oligomers using a modified mordenite based catalyst |
US5019357A (en) * | 1987-11-10 | 1991-05-28 | Mobil Oil Corporation | Reactor system for upgrading light olefins in staged reactors |
US4777316A (en) * | 1987-11-10 | 1988-10-11 | Mobil Oil Corporation | Manufacture of distillate hydrocarbons from light olefins in staged reactors |
US4788366A (en) * | 1987-12-28 | 1988-11-29 | Mobil Oil Corporation | Production of heavier hydrocarbons from light olefins in multistage catalytic reactors |
US4925995A (en) * | 1988-03-21 | 1990-05-15 | Shell Oil Company | Process for preparing liquid hydrocarbons |
US4939314A (en) * | 1988-12-19 | 1990-07-03 | Mobil Oil Corporation | Method for on-stream low-pressure regeneration of an oligomerization catalyst from a fluid-bed reactor operating at high pressure with hydrocarbons in a non-liquid phase |
US5234873A (en) * | 1989-03-03 | 1993-08-10 | Institut Francais Du Petrole | Catalyst with a mordenite base containing at least one metal of groups iia, ivb, iib or iva and its use in isomerization of a c8 aromatic cut |
US5177282A (en) * | 1989-05-05 | 1993-01-05 | Huels Aktiengesellschaft | Oligomerization of olefins |
US5043517A (en) * | 1989-10-30 | 1991-08-27 | Mobil Oil Corporation | Upgrading light olefin fuel gas in a fluidized bed catalyst reactor and regeneration of the catalyst |
US4971606A (en) * | 1989-11-06 | 1990-11-20 | Air Products And Chemicals, Inc. | Closed-loop thermal regeneration of adsorbents containing reactive adsorbates |
US4973790A (en) * | 1989-11-16 | 1990-11-27 | Mobil Oil Corporation | Process for upgrading light olefinic streams |
US5053579A (en) * | 1989-11-16 | 1991-10-01 | Mobil Oil Corporation | Process for upgrading unstable naphthas |
US5405814A (en) * | 1990-07-25 | 1995-04-11 | Mobil Oil Corporation | Olefin conversion catalyst regeneration |
US5057640A (en) * | 1991-01-02 | 1991-10-15 | Mobil Oil Corp. | Propylene oligomerization over silica modified zeolites |
US5198099A (en) * | 1991-08-12 | 1993-03-30 | Exxon Research And Engineering Company | Three-stage process for producing ultra-clean distillate products |
US5672800A (en) * | 1992-01-30 | 1997-09-30 | Exxon Chemical Patents Inc. | Alkene oligomerization |
US5430220A (en) * | 1993-05-03 | 1995-07-04 | Phillips Petroleum Company | Platinum and tin-containing catalyst and use thereof in alkane dehydrogenation |
US5624547A (en) * | 1993-09-20 | 1997-04-29 | Texaco Inc. | Process for pretreatment of hydrocarbon oil prior to hydrocracking and fluid catalytic cracking |
US5847252A (en) * | 1995-12-15 | 1998-12-08 | Uop Llc | Process for integrated oligomer production and saturation |
US5873994A (en) * | 1997-07-15 | 1999-02-23 | Phillips Petroleum Company | Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin |
US6281401B1 (en) * | 1999-09-16 | 2001-08-28 | Phillips Petroleum Company | Oligomerization of olefins |
US6864398B2 (en) * | 2000-04-03 | 2005-03-08 | Chevron U.S.A. Inc. | Conversion of syngas to distillate fuels |
US6500999B2 (en) * | 2000-05-26 | 2002-12-31 | Snamprogetti S.P.A. | Process for the production of hydrocarbons with a high octane number by means of the selective dimerization of isobutene with acid catalysts |
US6884914B2 (en) * | 2001-02-01 | 2005-04-26 | Exxon Mobil Chemical Patents Inc. | Olefin oligomerization |
US20080029437A1 (en) * | 2006-08-02 | 2008-02-07 | Exxonmobil Research And Engineering Company | Olefin upgrading process with guard bed regeneration |
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US11384035B2 (en) | 2019-08-21 | 2022-07-12 | Lg Chem, Ltd. | Oligomer preparation method and oligomer preparation device |
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US7956227B2 (en) | 2011-06-07 |
CA2707028C (en) | 2016-08-09 |
GB2467689B (en) | 2012-11-07 |
GB2467689A (en) | 2010-08-11 |
CA2707028A1 (en) | 2009-06-11 |
WO2009073395A1 (en) | 2009-06-11 |
MX2010006190A (en) | 2010-07-06 |
GB201008649D0 (en) | 2010-07-07 |
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